Hydrocracking catalyst comprising a layered clay type crystalline aluminosilicate component,a group viii component and rhenium and process using said catalyst



Oct. 20, 1970 3,535,230

AY TYPE ENT,AGROUP VIII COMPONENT AND RHENIUM AND PROCESS L AYERED CL J.R. KITTRELL HYDROCRACKING CATALYST COMPRISING A CRYSTALLINEALUMINOSILICA'IE COMPON USING SAID CATALYST Filed Nov lfi, 1968 4 M 6 4/5 G 6 m w N I I MM 2 RKN YAZ HR R 3 r F. u 7 0 o 2 w I w I 3 F. 1 a 9 OM 8 4 C 1 I, 8 n a HYDRO- TREATING ZONE FIG. 1

n n 1 L L E m x m a E m l T N 5 W. K 1 R L ACO d F Z T A Z V S E AR N Rcc II a F o 6 7 l o 5 5 4 w w 4 a O- 7 4 5 w 4 C C 1 Q 6 0 3 1 f 4 U 3 3O u- 4 3 2 H H 3 M H I N 4 G n u G -NE J mn- M N u D A 0 D c 0 Y 9 Ymz R4 H 8 HT c 4 I lllls v H FIG. 2

TORNEYS United States Patent 3,535,230 HYDROCRACKING CATALYST COMPRISINGA LAYERED CLAY TYPE CRYSTALLINE ALU- MINOSILICATE COMPONENT, A GROUP WIICOMPONENT AND RHENIUM AND PROCESS USING SAID CATALYST James R. Kittrell,El Cerrito, Califi, assignor to Chevron Research Company, San Francisco,Calif., a corporation of Delaware Filed Nov. 15, 1968, Ser. No. 776,043Int. Cl. 010g 37/00 U.S. Cl. 208-60 22 Claims ABSTRACT OF THE DISCLOSUREA hydrocracking catalyst comprising a layered claytype crystallinealuminosilicate cracking component, 0.01 to 2.0 weight percent, based onsaid cracking component and calculated as the metal, of a hydrogenatingcomponent selected from platinum and compounds thereof, palladium andcompounds thereof, and iridium and compounds thereof, and 0.01 to 2.0Weight percent, based on said cracking component and calculated as themetal, of a hydrogenating component selected from the group consistingof rhenium and compounds thereof, and processes using said catalyst.

INTRODUCTION This invention relates to catalytic hydrocracking ofhydrocarbons, including petroleum distillates and solventdeasphaltedre'sidua, to produce high-value fuel products, including gasoline.

PRIOR ART It is well known that a Wide variety of crystalline zeoliticmolecular sieves may be used as the cracking component of hydrocrackingcatalysts. It is also well known that the preferred, and most commonlyused, hydrogenating components associated with these zeolitic crackingsupports are platinum and palladium. Rabo et al. US. Pat. 3,236,761, forexample, provides a particular type of decationized zeolitic molecularsieve catalyst, which may be used in some reactions without addedmetals, and in some reactions with added metals. The various applicablereactions are isomerization, reforming, cracking, polymerization,alkylation, dealkylation, hydrogenation, dehydrogenation andhydrocracking. Rhenium is named as a metal with which the molecularsieve may be loaded, but it is not clear from the patent which reactionssuch a catalyst would be used to catalyze. No example of arhenium-molecular sieve catalyst is given, and the hydrocracking portionof the disclosure indicates that the molecular sieve catalyst of thepatent may be used for hydrocracking without added metals, butpreferably with added platinum or palladium if a metal-loaded molecularsieve is to be used. Further, because of the great stress placed by theRabo et al. patent on Group VIII metals in association with a molecularsieve cracking component, and particularly the noble metals, and theabsence of any interest in rhenium except a passing mention, there is noguide in the patent either as to the applicability of arhenium-molecular sieve catalyst for the hydrocracking reaction inparticular, or to the amount of rhenium such a catalyst should contain,or to the hydrocracking results that might be expected.

It is also known in the art to use 2 weight percent rhenium inassociation with a gel-type silica-alumina cracking component for thehydrocracking of hydrocarbon fractions. For example, Wilson US. Pat.3,278,418 makes such a disclosure. However, it is also known that such acatalyst has low hydrocracking activity, and that a silver 3,535,230Patented Oct. 20, 1970 promoter must be used with the rhenium to providea catalyst having acceptable activity. Accordingly, the Wilson patentindicates that the rhenium-silica-alumina catalyst of his Examples 1 and2 had activity indices of 42 and 47, respectively, whereas with theaddition of a silver promoter for the rhenium, activity indices as highas could be achieved. The data in the Wilson patent indicate that withrhenium levels as high as 2 weight percent, the rhenium-silica-aluminahydrocracking catalyst had only moderate hydrocracking activity. Ahigher hydrocracking activity would have been obtained with a higherrhenium level, but the cost of rheniummakes higher levels undesirable.Wilson was able partially to solve the problem of maintaining low levelsof rhenium and adequate hydrocracking activity by adding a secondhydrogenation component-silver-to the catalyst. However, this wasaccomplished only at a sacrifice in catalyst stability. As correctlyindicated by Wilson, a hydrocracking catalyst having a silica-aluminacracking component is extremely nitrogen-sensitive, and the hydrocarbonfeed hydrocracked in the presence of such a catalyst must be pretreatedto reduce the nitrogen content to a low level; more than minor amountsof nitrogen in the hydrocarbon feed have an intolerable poisoning effecton the acid sites of the cracking component of the catalyst, seriouslydiminishing cracking activity.

It is also known that a crystalline zeolitic molecular sieve crackingcomponent, while relatively insensitive to organic nitrogen compoundsand ammonia, has a wellordered and uniform pore structure as a result ofthe crystal structure having bonds that are substantially equally strongin three dimensions. This provides definite limitations on the access ofreactant molecules to the interiors of the pores.

It is also known, particularly from Granquist US. Pat. 3,252,757, that arelatively new crystalline aluminosilicate that has been synthesized hasthe empirical formula nSiO A1 0 mAB :xH O

where the layer lattices comprise said silica, said alumina, and said B,and where n is from 2.4 to 3.0

m is from 0.2 to 0.6

A is one equivalent of an exchangeable cation having a valence notgreater than 2, and is external to the lattice,

B is chosen from the group of negative ions which consists of F, OH*,/20 r and mixtures thereof, and is internal in the lattice, and

x is from 2.0 to 3.5 at 50% relative humidity,

said mineral being characterized by a d spacing at said humidity withinthe range which extends from a lower limit of about 10.4 A. to an upperlimit of about 12.0 A.

when A is monovalent, to about 14.7 A. when A is divalent, and to avalue intermediate between 12.0 A.

and 14.7 A. when A includes both monovalent and divalent cations. Theequivalent of an exchangeable cation,

A, in said catalyst may be chosen from the group consisting of H+, NHJ,Na Li+, K /2Ca++, /2Mg++,

/2Sr++, and /2Ba++, and mixtures thereof.

Said synthetic aluminosilicate mineral is a layered clay-typecrystalline aluminosilicate, which term as used herein is intended toinclude dried and calcined forms as well as undried forms of saidsynthetic mineral, similar synthetic minerals, and correspondingidentical and similar natural minerals.

Said aluminosilicate mineral in dried and calcined form is known fromUS. Pat. 3,252,889 to have application as a component of a catalyticcracking catalyst; however, applications of said mineral as a component,in dried or calcined form or otherwise of a hydrocracking catalyst havenot been disclosed heretofore.

OBJECTS In view of the foregoing, objects of the present inventioninclude providing a novel catalyst useful for hydrocracking, and a novelhydrocracking process using said catalyst, said catalyst:

(1) Having a cracking component less sensitive to nitrogen poisoningthan silica-alumina gel;

(2) Having a cracking component that is crystalline in structure, havingpores elongated in two directions, contrary to the pores of crystallinezeolitic molecular sieves, and therefore having less reactant accesslimitations than the pores of such molecular sieves;

(3) Having a first hydrogenating component providing increased activityand stability to said catalyst, compared with a similar catalyst notcontaining said component;

(4) Having a second hydrogenating component providing additionalstability to said catalyst, compared with the same catalyst whichcontains said first hydrogenating component but not said secondhydrogenating component.

It is a further object of the present invention to provide variousembodiments of a hydrocracking process using a catalyst having theaforesaid characteristics, including methods of further improvingcatalyst stability, and methods of operating the hydrocracking processin an integrated manner with other process units to achieve variousadvantageous results.

The present invention will best be understood, and further objects andadvantages thereof will be apparent, from the following description whenread in connection with the accompanying drawing.

DRAWING In the drawing, FIG. 1 is a diagrammatic illustration ofapparatus and flow paths suitable for carrying out the process ofseveral of the embodiments of the present in- STATEMENT OF INVENTION Ithas been found that a catalyst comprising a layered clay-typecrystalline aluminosilicate cracking component,

namely the layered synthetic clay-type crystalline aluminosilicatemineral of Granquist U.S. Pat. 3,252,757, a hydrogenating componentselected from platinum and compounds thereof, palladium and compoundsthereof,

and iridium and compounds thereof, in an amount of .p

0.01 to 2.0 weight percent, calculated as metal, and a rhenium orrhenium compound hydrogenating component in an amount of 0.01 to 2.0weight percent, calculated as metal and based on said crackingcomponent, has all of the desirable catalyst attributes listed underObjects above and, therefore, in accordance with the present inventionthere is provided such a catalyst and a hydrocracking process using sucha catalyst. It is not obvious from Rabo et al. U.S. Pat. 3,236,761 thata rhenium-crystalline zeolitic molecular sieve catalyst has applicationas a hydrocracking catalyst, or what rhenium levels such a catalystshould contain. It is even less obvious from Rabo et al. that not onlyshould rhenium be used as a component of a hydrocracking catalyst, butthat the layered synthetic crystalline aluminosilicate mineral ofGranquist U.S. Pat. 3,252,757 could be used instead of a crystallinezeolitic molecular sieve. Even if such matters were clear from Rabo etal., Wilson U.S. Pat. 3,278,418 would lead a man skilled in the art toconclude that such a catalyst would either need to contain considerablymore than 2 weight percent rhenium or that it must contain a silverhydrogenating component to obtain adequate hydrocracking activity. Ithas been found that neither of these conclusions is correct; Wilson alsowould lead a man skilled in the art to conclude, even if he considereduse for hydrocracking of the catalyst used in the process of the presentinvention that use of a hydrogenating component in addition to rhenium,to enable the catalyst to maintain adequate hydrocracking activity atacceptably low rhenium levels, would cause the catalyst stability tosuffer markedly. This conclusion also is not correct. Accordingly, ithas been found that the catalyst of the present invention surprisinglyprovides advantages over the Rabo et al. platinum or palladium onmolecular sieve hydrocracking catalyst and the Wilsonrhenium-silica-alumina hydrocracking catalyst, while unexpectedly beingfree from disadvantages that the art would lead one to expect. Inparticular, in the catalyst of the present invention: (1) the presenceof the rhenium component results in a catalyst of higher stability thana catalyst that is identical, except that contains no rhenium; and (2)the presence of the component selected from platinum and compoundsthereof, palladium and compounds thereof, and iridium and compoundsthereof results in a catalyst of higher activity and stability than acatalyst that is identical except that contains no such Group VIIIcomponent.

In accordance with the present invention, therefore, there is provided ahydrocracking catalyst comprising a layered, clay-type crystallinealuminosilicate cracking component, 0.01 to 2.0 weight percent, based onsaid cracking component and calculated as the metal, of a hydrogenatingcomponent selected from platinum and compounds thereof, palladium andcompounds thereof, and iridium and compounds thereof, and 0.01 to 2.0weight percent, based on said cracking component and calculated as themetal, of a hydrogenating component selected from rhenium and compoundsthereof, said layered aluminosilicate having, prior to drying andcalcining of said catalyst the empirical formula where the layerlattices comprise said silica, said alumina, and said B, and where it isfrom 2.4 to 3.0

m is from 0.2 to 0.6

A is one equivalent of an exchangeable cation having a valence notgreater than 2, and is external to the lattice,

B is chosen from the group of negative ions which consists of F1 OH, /20and mixtures thereof, and is internal in the lattice, and

x is from 2.0 to 3.5 at 50% relative humidity,

said material being characterized by a spacing at said humidity withinthe range which extends from a lower limit of about 10.4 angstroms to anupper limit of about 12.0 angstroms when A is monovalent, to about 14.7angstroms when A is divalent, and to a value intermediate between 12.0angstroms and 14.7 angstroms when A includes both monovalent anddivalent cations.

Further in accordance with the prevent invention there is provided acatalyst effective for various hydrocarbon conversion reactions,including hydrocracking, hydrodesulfurization, hydrodenitrification,hydrogenation and hydroisomerization, comprising:

(A) A layer-type, crystalline, clay-like mineral cracking componentwhich prior to drying and calcining of said catalyst has the empiricalformula nSiO :Al O :mAB:xH O

where the layer lattices comprise said silica, said alumina, and said B,and where n is from 2.4 to 3.0 m is from 0.2 to 0.6 A is one equivalentof an exchangeable cation having a valence not greater than 2, and isexternal to the lattice,

B is chosen from the group of negative ions which consists of F-, H1 /zOand mixtures thereof, and is internal in the lattice, and

x is from 2.0 to 3.5 at 50% relative humidity,

said mineral being characterized by a (1 spacing at said humidity withinthe range which extends from a lower limit of about 10.4 A. to an upperlimit of about 12.0 A. when A is monovalent, to about 14.7 A. when A isdivalent, and to a value intermediate between 12.0 A. and 14.7 A. when Aincludes both monovalent and divalent cations, and

(B) A hydrogenating component selected from platinum and compoundsthereof, palladium and compounds thereof, and iridium and compoundsthereof, in an amount of 0.01 to 2.0 weight percent, based on saidcracking component and calculated as metal, and a hydrogenatingcomponent selected from rhenium and compounds thereof, in an amount of0.01 to 2.0 weight percent, based on said cracking component andcalculated as metal.

Said cracking component may be present in said catalyst in an amount of10 to 99.9 weight percent, based on the total catalyst. If desired, saidcatalyst may further comprise a crystalline zeolitic molecular sievecracking component in the amount of 1 to 50 weight percent, based on thetotal catalyst. The equivalent of an exchangeable cation, A, in saidcatalyst may be chosen from the group consisting of H+, NH Na+, Li+, K'/2Ca++,' /2Mg++, AzSr and /2Ba+"", and mixtures thereof.

Said catalyst additionally may comprise a component selected from thegroup consisting of alumina and silicaalumina and a hydrogenatingcomponent selected from the group consisting of Group VI metals andcompounds thereof and nickel and compounds thereof. When the catalystcomprises alumina or silica-alumina, titania advantageously may bepresent also. When the catalyst comprises nickel or a compound thereof,tin or a compound thereof advantageously may be present also. When saidcatalyst comprises said additional components, preferably the catalystis prepared by coprecipitation of all non-crystalline components to forma slurry, followed by addition of the layered clay-type crystallinealuminosilicate component (and additionally a crystalline zeoliticmolecular sieve component, if desired) to the slurry in particulateform, followed by filtering, washing and drying to produce a hydrogelmatrix having said crystalline component (or components) dispersedtherethrough. Preferably the finished catalyst will have substantiallyall of the catalytic metal or metals located in the matrix, and saidcrystalline component (or components) will be substantially in theammonia or hydrogen form, and will be substantially free of catalyticloading metal or metals; that is, said crystalline component (orcomponents) will contain less than about 0.5 weight percent of catalyticmetal or metals. This result will obtain if addition of said crystallinecomponent (or components) to the slurry of other catalyst components isaccomplished at a pH of 5 or above.

Further in accordance with the present invention, there is provided ahydrocracking process which comprises contacting a hydrocarbon feedstockcontaining substantial amounts of materials boiling above 200 F. andselected from the group consisting of petroleum distillates,solventdeasphalted petroleum residua, shale oils and coal tardistillates, in a reaction zone with hydrogen and the aforesaid catalystcomprising a layered clay-type crystalline aluminosilicate athydrocracking conditions including a temperature in the range 400 to 950F., a pressure in the range 800 to 3500' p.s.i.g., a liquid hourly spacevelocity in the range 0.1 to 5.0, and a total hydrogen supply rate of200 to 20,000 s.c.f. of hydrogen per barrel of said feedstock, andrecovering from said reaction zone valuable products, includinggasoline. The hydrogen feedstock preferably contains less than 1000 ppm.organic nitrogen. A prior hydrofining step may be used, if desired, toreduce the feed nitrogen content to the preferred level; however,because of the superior nitrogen tolerance of the layered clay-typecrystalline aluminosilicate component, compared with silica-alumina, thehydrofining step need not accomplish complete nitrogen contentreduction, as further discussed hereinafter.

Further in accordance with the present invention, advantageous resultsare obtained by providing in the reaction zone, in addition to saidcatalyst comprising a layered clay-type crystalline aluminosilicate, aseparate second catalyst comprising a hydrogenating component selectedfrom Group VI metals and compounds thereof, a hydrogenating componentselected from Group VIII metals and compounds thereof, and a componentselected from the group consisting of alumina and silica-alumina.Further in accordance with the present invention, said separate secondcatalyst may be located in said reaction zone in a bed disposed abovesaid catalyst comprising a layered clay-type crystalline aluminosilicatecracking component. In the embodiments of the present inventiondiscussed in this paragraph, no other prior hydrofining step generallywill be necessary, because hydrofining is accomplished in one reactionzone concurrently with hydrocracking, together with some hydrogenationof aromatics.

Still further in accordance with the present invention, there isprovided a hydrocracking process which comprises sequentially contactinga hydrocarbon feedstock and hydrogen with a first bed of catalyst andthen with a second bed of catalyst, said catalyst beds both beinglocated within a single elongated reactor pressure shell, said first bedof catalyst being located in an upper portion of said shell, thecatalyst of said first bed comprising a hydrogenating component selectedfrom the group consisting of Group VI metals and compounds thereof andGroup VIII metals and compounds thereof, and a component selected fromthe group consisting of alumina and silica-alumina, the catalyst of saidsecond bed being said catalyst comprising a layered clay-typecrystalline aluminosilicate, maintaining said first bed of catalyst andsaid second bed of catalyst at a temperature in the range of 400 to 950F. and a pressure in the range 800 to 3500 p.s.i.g. during saidcontacting, maintaining the total supply rate of said hydrogen into saidreactor shell from 200 to 20,000 s.c.f. of hydrogen per barrel of saidfeedstock, and recovering a gasoline product from the effiuent of saidsecond bed of catalyst.

The hydrocracking zone of the process of the present invention may beoperated once through, or advantageously may be operated by recyclingthereto materials from the effluent thereof that boil above 200 F.,preferably above 400 F. All or a portion of these heavier materialsadvantageously may be catalytically cracked. The heavy gasoline fractionfrom the hydrocracking zone advontageously may be catalyticallyreformed.

HYDROCARBON FEEDSTOCKS The feedstocks supplied to the hydrocracking zonecontaining said catalyst comprising a layered clay-type crystallinealuminosilicate in the process of the present invention are selectedfrom the group consisting of petroleum distillates, solvent-deasphaltedpetroleum residua, shale oils and coal tar distillates. The feedstockscontain substantial amounts of materials boiling above 200 F.,preferably substantial amounts of materials boiling in the range 350 to950 F., and more preferably in the range 400 to 900 F. Suitablefeedstocks include those heavy distillates normally defined as heavystraight-run gas oils and heavy cracked cycle oils, as well asconventional FCC feed and portions thereof. Cracked stocks may beobtained from thermal or catalytic cracking of various stocks, including those obtained from petroleum, gilsonite, shale and coal tar. Asdiscussed hereinafter, the feedstocks may have been subjected to ahydrofining and/or hydrogenation treatment, which may have beenaccompanied by some hydrocracking, before being supplied to the hydrocracking zone containing said catalyst comprising a layered clay-typecrystalline aluminosilicate.

NITROGEN CONTENT OF FEEDSTOCKS While the process of the presentinvention can be practiced with utility when supplying to thehydrocracking zone containing a catalyst comprising a layered clay-typecrystalline aluminosilicate, hydrocarbon feeds containing relativelylarge quantities of organic nitrogen, for example several thousand partsper million organic nitrogen, it is preferred that the organic nitrogencontent be less than 1000 parts per million organic nitrogen. Apreferred range is 0.5 to 1000 parts per million; more preferably, 0.5to 100 parts per million. As previously discussed, a prior hydrofiningstep may be used, if desired, to reduce the feed nitrogen content to thepreferred level. The prior hydrofining step advantageously may alsoaccomplish hydrogenation and a reasonable amount of hydrocracking.Because of the superior tolerance of the layered clay-type crystaL linealuminosilicate component for organic nitrogen compounds, compared withsilico-alumina, the hydrofining step need not accomplish completeorganic nitrogen content reduction. Further, because of the superiortolerance of said component for ammonia, compared with silica-alumina,and because said component is more tolerant of ammonia than of organicnitrogen compounds, ammonia produced in the hydrofining zone either maybe removed from the system between the hydrofining Zone and thehydrocracking zone containing the hydrocracking catalyst comprising saidcomponent, or may be permitted to pass into the hydrocracking zone alongwith the feed thereto.

SULFUR CONTENT OF FEEDSTOCK While the process of the present inventioncan be practiced with utility when supplying to the hydrocracking zone,containing a catalyst comprising a layered claytype crystallinealuminosilicate, hydrocarbon feeds containing relatively largequantities of organic sulfur, it is preferable to maintain the organicsulfur content of the feed to that zone in a range of to 3 weightpercent, preferably 0 to 1 weight percent.

CATALYST COMPRISING A LAYERED CLAY-TYPE CRYSTALLINE ALUMINOSILICATE C OM P O- NENT, A RHENIUM OR RHENIUM COMPOUND HYDROGENATING COMPONENT, ANDA HY- DROGENATING COMPONENT SELECTED FROM PLATINUM AND COMPOUNDSTHEREOF, PAL- LADIUM AND COMPOUNDS THEREOF, AND

IRIDIUM AND COMPOUNDS THEREOF (A) General The layered clay-typecrystalline aluminosilicate used in preparing the catalyst is thesynthetic mineral described above and in Granquist U.S. Pat. 3,252,757is preferred. This component will be present in the catalyst in anamount of to 99.9 Weight percent, based on the total catalyst.

The rhenium hydrogenating component of the catalyst may be present inthe final catalyst in the form of the metal, metal oxide, metal sulfide,or a combination thereof. The rhenium or compound thereof may becombined with the layer clay-type crystalline aluminosilicate crackingcomponent, or may be combined with other catalyst components in whichsaid cracking component is dispersed, or both. In any case, the rheniumwill be present in an amount of 0.01 to 2.0 weight percent, based onsaid cracking component and calculated as the metal.

When a conventional crystalline zeolitic molecular sieve crackingcomponent is included in the catalyst, said molecular sieve crackingcomponent may be of any type that is known in the art as a usefulcomponent of a conventional hydrocracking catalyst comprising a noblemetal or noble metal-compound hydrogenating component. A

decationized molecular sieve cracking component is preferred. Especiallysuitable are faujasite, particularly Y" type and X type faujasite, andmordenite, in the ammonia form, hydrogen form, alkaline earth-exchangedform, or rare earth-exchanged form.

The hydrogenating component of the catalyst that is selected fromplatinum, palladium, iridium, and compounds of platinum, palladium andiridium may be present in the final catalyst in the form of the metal,metal oxide, metal sulfide, or a combination thereof. This component maybe combined with the layerered clay-type crystalline aluminosilicatecracking component, or may be combined with other catalyst components inwhich said aluminosilicate cracking component is dispersed, or both. Inany case, the component will be present in an amount of 0.01 to 2.0weight percent, based on said aluminosilicate cracking component andcalculated as the metal.

A preferred catalyst comprises said layered clay-type crystallinealuminosilicate cracking component intimately dispersed in a matrix ofother catalytic components comprising alumina, silica-alumina, orsilica-alumina-titania. The rhenium or compound thereof, and theplatinum, palladium or iridium, or compound of platinum, palla dium oriridium may be combined with said alumino silicate cracking componentbefore the latter is dispersed in the matrix, or the rhenium or compoundthereof and the platinum, palladium or iridium, or compound of platinum,palladium or iridium may be a portion of the matrix. Examples ofsuitable matrices, in addition to matrices consisting of alumina orsilica-alumina, include matrices comprising: (a) palladium or a compoundthereof and rhenium or a compound thereof and silicaalumina; (b)palladium or a compound thereof and rhenium or a compound thereof andalumina; (c) iridium or a compound thereof and rhenium or a compoundthereof and alumina; (d) iridium or a compound thereof and rhenium or acompound thereof and silicaalumina; (e) platinum or a compound thereofand rhenium or a compound thereof and silica-alumina; (f) any of theforegoing with the addition of nickel or a compound thereof or nickel ora compound thereof plus tin or a compound thereof; if desired, thenickel or compound thereof may be accompanied by a Group VI metal orcompound thereof.

(B) Method of preparation The layered clay-type crytallinealuminosilicate cracking component of the catalyst may be prepared inthe manner set forth in Granquist U.S. Pat. 3,252,757.

In the case wherein rhenium or a compound thereof and platinum,palladium or iridium, or compounds of platinum, palladium or iridium areadded directly to the layered clay-type crystalline aluminosilicatecracking component, impregnation using aqueous solutions of suitablehydrogenating metal compounds or adsorption of suitable hydrogenatingmetal compounds are operable methods of incorporating the hydrogenatingcomponents or compounds thereof into said aluminosilicate component. Ionexchange methods whereby the hydrogenating components are incorporatedinto said aluminosilicate component by exchanging those components witha metal component already present in said aluminosilicate component maybe used. However, such methods require use of compounds wherein themetals to be introduced into said aluminosilicate component are presentas cations. Compounds wherein rhenium is present as a cation are notcommonly available in aqueous solution.

In the case wherein said aluminosilicate cracking component first isdispersed in a matrix of other catalytic components and rhenium or acompound thereof and platinum, palladium or iridium, or a compound ofplatinum, palladium or iridium are introduced into the resultingcomposition, impregnation using an aqueous solution of suitablehydrogenating component compounds or adsorption of suitablehydrogenating component compounds are the preferred methods.

The rhenium compound used in the impregnation or adsorption stepgenerally will contain rhenium in anionic form. The compound should beone that is soluble in water, and that contains no ions that are knownas contaminants in hydrocracking catalysts. Suitable rhenium compoundsare perrhenic acid, HReO and ammonium perrhenate, NH ReO Impregnationalso may be accomplished with an ammoniacal solution of rheniumheptoxide.

The platinum, palladium or iridium compound used in preparing thecatalyst may be any convenient compound, for example platinum, palladiumor iridium chloride, tetra ammino palladium nitrate, etc.

Where the layered clay-type crystalline aluminosilicate component, withor without added hydrogenating components, is dispersed in a matrix ofother catalyst components, the dispersion may be accomplished bycogelation of said other components around said aluminosilicatecomponent in a conventional manner.

Following combination of the catalyst components, the resultingcomposition may be washed free of impurities and dried at a temperaturein the range 500 to 1200 F., preferably 900 to 1150 F., for a reasonabletime, for example 0.5 to 48 hours, preferably 0.5 to 20 hours.

The finished catalyst may be sulfided in a conventional manner prior touse, if desired. If not presulfided, the catalyst will tend to becomesulfided during process op eration from any sulfur compounds that may bepresent in the hydrocarbon feed. As discussed elsewhere herein, theequilibrium degree of sulfiding at a given operating temperature will bedifferent than in a corresponding catalytic system wherein a noble metalcomponent alone is present, with no rhenium being present.

SEPARATE HYDROFINING CATALYST (A) General As previously indicated,advantageous results are obtained by providing in the reaction zonecontaining the hydrocracking catalyst of the present invention aseparate second catalyst comprising a hydrogenating component selectedfrom Group VI metals and compounds thereof, a hydrogenating componentselected from Group VIII metals and compounds thereof, and a supportselected from the group consisting of alumina and silica-alumina.Pellets or other particles of this separate second catalyst may bephysically mixed with said hydrocracking catalyst, but preferably aredisposed in a separate catalyst bed located ahead of said hydrocrackingcatalyst in the same reactor shell, eliminating interstage condensation,pressure let-down and ammonia and hydrogen sulfide removal. In apreferred arrangement using downfiow of hydrocarbon feed, the bed ofseparate second catalyst is located above said hydrocracking catalyst inthe same reactor shell.

Where said separate second catalyst is located in the same reactor shellas the hydrocracking catalyst of the present invention, it is preferablypresent in an amount in the range of to 40 volume percent of the totalamount of catalyst in the reactor.

In an arrangement less preferred than the ones discussed above in thissection, the separate second catalyst may be located in a separatehydrofining reactor, operated under conventional hydrofining conditions,from the effiuent of which ammonia or hydrogen sulfide, or both, andalso hydrocarbon products, if desired, may be removed prior tohydrocracking the remaining hydrofined feedstock in a subsequenthydrocracking reactor in the presence of the catalyst of the presentinvention.

In any of the arrangements discussed in this section, the separatesecond catalyst preferably has hydrofining activity and hydrogenationactivity, and even more preferably also has enough hydrocrackingactivity to convert 0.2 to 50, preferably 5 to 20, weight percent of thehydrocarbon feedstock to products boiling below the initial boilingpoint of the feedstock in a single pass. The hydrogenation activitypreferably is sufficient to saturate or partially saturate a substantialportion of the organic oxygen, nitrogen and sulfur compounds in the feedto Water, ammonia and hydrogen sulfide.

Preferably, said separate second catalyst contains nickel or cobalt orcompounds thereof in an amount of 1 to 15 Weight percent, calculated asmetal, and molybdenum or tungsten or compounds thereof, in an amount of5 to 30 Weight percent, calculated as metal, with the remainder of thecatalyst consisting of alumina, or silicaalumina containing up to 50weight percent silica.

Particularly preferred examples of said separate second catalyst,comprising silica-alumina, are:

Percent by weight of total catalyst,

calculated as metal SiOz/AlzOa N1 M0 W weight ratio Said separate secondcatalyst may be prepared by any conventional preparation method,including impregnation of an alumina or silica-alumina support withsalts of the desired hydrogenating component, or cogelation of allcomponents, with the latter method being preferred.

As previously pointed out, the hydrocracking catalyst of the presentinvention has activity and stability advantages over a hydrocrackingcatalyst comprising rhenium and a gel-type silica-alumina. It has beenfound that use of said separate second catalyst in the above-describedarrangements further increases the stability of the hydrocrackingcatalyst of the present invention, compared with the stability of thelatter catalyst when the identical feed thereto has not been first orconcurrently processed in the presence of said separate second catalyst.

OPERATING CONDITIONS The hydrocracking zone containing the catalyst ofthe present invention is operated at hydrocracking conditions includinga temperature in the range 400 to 950 F., preferably 500 to 850 F., apressure in the range 800 to 3500 ps.i.g., preferably 1000 to 3000ps.i.g., a liquid hourly space velocity in the range 0.1 to 5.0,preferably 0.5 to 5.0, and more preferably 0.5 to 3.0. The totalhydrogen supply rate (makeup and recycle hydrogen) to said zone is 200to 20,000 s.c.f., preferably 2000 to 20,000 s.c.f., of hydrogen perbarrel of said feedstock.

Where a separate hydrofining zone, which also may accomplishhydrogenation and some hydrocracking, is located ahead of thehydrocracking zone containing the catalyst of the present invention, theoperating conditions in the separate hydrofining zone include atemperature of 400 to 900 F., preferably 500 to 800 F., a pressure of800 to 3500 ps.i.g., preferably 1000 to 2500 ps.i.g., and a liquidhourly space velocity of 0.1 to 5.0, preferably 0.5 to 3.0. The totalhydrogen supply rate (makeup and recycle hydrogen) is 200 to 20,000s.c.f. of hydrogen per barrel of feedstock, preferably 2000 to 20,000s.c.f. of hydrogen per barrel of feedstock.

Where a separate bed of hydrofining catalyst is located above a bed ofthe hydrocracking catalyst of the present invention in the same reactorshell, the space velocity through the bed of hydrofining catalyst willbe a function of the space velocity through the hydrocracking catalystbed and the amount of hydrofining catalyst expressed as a volume percentof the total catalyst in the reactor. For example, where the hydrofiningcatalyst is 25 volume percent of the total catalyst in the reactor, andthe space velocity through the bed of hydrocracking catalyst is 0.9, thespace velocity through the bed of hydrofining catalyst will be 2.7.Accordingly, the space velocity through the bed of hydrofining catalystin the process of the present invention may range from 0.15 to 45.0.

The operating conditions in the reforming zone and catalytic crackingzone employed in various embodiments of the present invention areconventional conditions known in the art.

PROCESS OPERATION WITH REFERENCE TO DRAWING Referring now to FIG. 1 ofthe drawing, in accordance with a primary embodiment of the presentinvention, a

hydrocarbon feedstock as previously described, which in this case mayboil above 400 F., is passed through line 1 into hydrocracking zone 2,which contains a hydrocracking catalyst comprising said layeredclay-type crystalline aluminosilicate cracking component, 0.01 to 2.0weight percent, based on said cracking component, of platinum, palladiumor iridium, and 0.01 to 2.0 weight percent, based on said crackingcomponent, of rhenium. As previously discussed, said layeredaluminosilicate component may be dispersed in a matrix of other catalystcomponents, which matrix may contain all or a portion of thehydrogenating components. Also as previously discussed, a separatesecond catalyst, previously described, may be located in hydrocrackingzone 2. The feedstock is hydrocracked in hydrocracking zone 2 atconditions previously discussed, in the presence of hydrogen suppliedthrough line 3. From hydrocracking zone 2 an effluent is withdrawnthrough line 4, hydrogen is separated therefrom in separator 5, andhydrogen is recycled to hydrocracking zone 2 through line 6. Fromseparator 5, hydocracked materials are passed through lines 7 and 8 todistillation column 9, where they are separated into fractions,including a C; fraction which is withdrawn through line 10, a C l80 F.fraction which is withdrawn through line 11, and a l80-400 F. fractionwhich is withdrawn through line 12.

Still referring to FIG. 1, in accordance with another embodiment of thepresent invention, the 180-400 F. fraction in line 12 is reformed underconventional catalytic reforming conditions in reforming zone 13, fromwhich a catalytic reformate is withdrawn through line 14.

Still referring to FIG. 1, in accordance with another embodiment of thepresent invention, a hydrocarbon feedstock which is to be hydrofinedand/or hydrogenated, and partially hydrocracked, if desired, in aseparate hydrotreating zone prior to being hydrocracked in hydrocrackingzone 2, is passed through line 15 to hydrotreating zone 16 containing acatalyst, as previously described, having hydrofining and/orhydrogenation activity. The feedstock is hydrotreated in zone 16 atconditions previously described, in the presence of hydrogen suppliedthrough line 17. The efiluent from hydrotreating zone 16 is passedthrough line 18 to separation zone 19, from which hydrogen separatedfrom the treated feedstock is recycled through line 20 to hydrotreatingzone 16. In zone 19, water entering through line 21 is used to scrubammonia and other contaminants from the incoming hydrocarbon stream, andthe ammonia, water and other contaminants are withdrawn from zone 19through line 22. The scrubbed feedstock is passed through line 8 todistillation column 9 and thence to hydrocracking zone 2.

Referring now to FIG. 2, a hydrocarbon feedstock, as previouslydescribed, which in this case may boil above 400 F., is passed throughline 29 to hydrotreating zone 30 containing a catalyst, as previouslydescribed, having hydrofining and/or hydrogenation activity. Thefeedstock is hydrofined and/or hydrogenated, and partially hydrocracked,if desired, in zone 30, at conditions previously described, in thepresence of hydrogen supplied through line 31. The efiluent from zone 30is passed through line 32, without intervening impurity removal, intohydrocracking zone 33, where it is hydrocracked in the presence of saidhydrocracking catalyst comprising a layered claytype crystallinealuminosilicate cracking component and 0.01 to 2.0 weight percent, basedon said cracking component, of platinum, palladium or iridium, and 0.01to 2.0 weight percent, based on said cracking component, of rhenium.Said catalyst may contain other catalytic components, and a separatesecond catalyst may be present in zone 33, as described in connectionwith zone 2 in FIG. 1. Hydrotreating zone 30 and hydrocracking zone 33may be located in separate reactor shells, which may be operated atdifferent pressures. Alternatively, and in a preferred manner ofoperation, hydrotreating zone 30 and hydrocracking zone 33 may beseparate catalyst beds located in a single pressure shell 34, and theeffluent from zone 30 may be passed to zone 33 without interveningpressure letdown, condensation or impurity removal. The effluent fromzone 33 is passed through line 35 to separation zone 36, from whichhydrogen is recycled through line 37 to hydrotreating zone 30. All or aportion of the recycled hydrogen may be passed through line 38 tohydrocracking zone 33, if desired. In separation zone 36, water enteringthrough line 40 is used to scrub ammonia and other contaminants from theincoming hydrocarbon stream, and the ammonia, water and othercontaminants are withdrawn from zone 36 through line 41. The eflluentfrom zone 36 is passed through line 42 to distillation column 43, whereit is separated into fractions, including a C; fraction which iswithdrawn through line 44, a C l80 F. fraction which is withdrawnthrough line 45, a l80400 F. fraction which is withdrawn through line46, and a fraction boiling above 400 F. which is withdrawn through line47. The fraction in line 47 may be recycled through lines 48 and 49 tohydrocracking zone 33. All or a portion of the fraction in line 48 maybe recycled to hydrotreating zone 30 through line 50, if desired.

Still referring to FIG. 2, in accordance with another embodiment of thepresent invention, the l80-400 F. fraction in line 46 may be passed to acatalytic reforming zone 55, where it may be reformed in the presence ofa conventional catalytic reforming catalyst under conventional catalyticreforming conditions to produce a catalytic reformate, which iswithdrawn from zone through line 56.

Still referring to FIG. 2, in another embodiment of the presentinvention, all or a portion of the fraction in line 47 may be passedthrough line 57 to catalytic cracking zone 58, which may contain aconventional catalytic cracking catalyst and which may be operated underconventional catalytic cracking conditions, and from which acatalytically cracked efliuent may be withdrawn through line 59.

EXAMPLES The following examples are given for the purpose of furtherillustrating the practice of the process of the present invention.However, it is to be understood that these examples are not intended inany way to limit the scope of the present invention.

Example 1 A catalyst consisting of rhenium and a layered claytypecrystalline aluminosilicate (Catalyst A, a comparison catalyst) wasprepared in the following manner.

These starting materials were used:

(1) 500 grams of a layered synthetic crystalline aluminosilicate mineralas described in Granquist US. Pat. 3,252,757;

(2) 1000 cc. of an aqueous solution of perrhenic acid (HReO containing10.8 grams of rhenium.

The mineral, in lumpy powder form, was introduced into a Hobart kitchenblender, followed by slow addition of the perrhenic acid solution whilestirring, to form a pasty mass. The pasty mass was transferred to a dishand dried at 150 F. for approximately 16 hours. The resulting driedmaterial was pressed through a 60-mesh screen to obtain fine granules.The granules were blended with a 1% Sterotex lubricant binder, andtabletted. The tablets were calcined in flowing air for 2 hours at 950F. The tabletted, calcined, rheninm-containing material was crushed, anda resulting 8-l6 mesh fraction thereof was separated for use as acatalyst in the process of the present invention. This catalystcontained an amount of rheninm approaching the theoretical amount basedon the amounts of ingredients used. This indicates that, althoughrheninm oxides normally are quite volatile, in this method ofpreparation only a small amount of rheninm is lost during drying andcalcination.

Example 2 A layered aluminosilicate-palladium catalyst (Catalyst B, acomparison catalyst) was prepared in the following manner.

These starting materials were used:

(1) 500 grams of a layered clay-type aluminosilicate mineral asdescribed in Granquist US. Pat. 3,252,757, in finely divided form.

(2) 6.8 grams of tetra ammino palladium nitrate [Pd(NH ](NO dissolved in700 ml. of H 0.

The layered aluminosilicate in powder form was mixed with the tetraammino palladium nitrate solution, to form a pasty mass. The pasty masswas dried in a vacuum oven for 6 hours at room temperature, then at200-250 F. for approximately 16 hours. The resulting material wastabletted, and then calcined in flowing dry air for 4 hours at 460 F.,then for 4 hours at 900 F. The resulting catalyst upon analysis wasfound to contain 0.5 weight percent palladium, calculated as metal.

Example 3 Example 4 The catalysts of the above examples were used tohydrocrack a portion of a light catalytic cycle oil feedstock of thefollowing description:

Gravity, API 30.1 Aniline Point, F. 132 Sulfur content, p.p.m

Nitrogen content, p.p.m. 0.3 ASTM D-1l60 Distillation:

ST/S 409/446 The hydrocracking was accomplished, on a recycle liquidbasis, at a pressure of 1200 p.s.i.g., a liquid hourly space velocity of0.9, a per-pass conversion of 60 liquid volume percent below 400 F., anda hydrogen supply rate of approximately 7000 s.c.f./bbl. The followingresults were obtained:

Catalyst Starting temperature, T. 566 490 500 Fouling rate, F./hr 0. 060. 11 0.02 05 liquid yield, wt. percent 91. 5 90 91. 5 Temperature after1,000 hrs., F 626 600 520 Of these catalysts, Catalyst C is thesupperior catalyst, because its low fouling rate far offsets itsslightly lower activity. After only 1000 hours operation, Catalyst C ismore active than Catalyst B, more active than Catalyst A, and has alower fouling rate than either. Furthermore, use of Catalyst C resultsin a significantly higher C gasoline yield than Catalyst B.

Example 5 The l-400 F. portion of the product of Example 4, resultingfrom use of Catalyst C, is catalytically reformed, using a conventionalreforming catalyst and conventional reforming conditions, and is foundto be a superior feedstock for this operation. The catalytic re formateis combined with the C F. portion of the product of Example 4, toproduce a gasoline pool.

Example 6 The 400 F.+ portion of the product of Example 4, resultingfrom use of Catalyst C, is recycled to the catalytic cracking unit whichproduced the light cycle oil feed used in Example 4. This upgrades thetotal feed to the catalytic cracking unit, and causes decreased cokeproduction and increased gasoline production in that unit. Theseimproved results are made possible because of the improvedcharacteristics of the 400 F.+ materials recycled from the hydrocrackingzone to the catalytic cracking unit, compared with the approximately 400F.+ light cycle oil supplied to the hydrocracking zone from th catalyticcracking unit.

Example 7 A catalyst prepared exactly as in Example 3, and having thesame composition as Catalyst C of Example 3, is used to hydrocrackanother portion of the same light cycle oil hydrocarbon feedstock thatis referred to in Example 4. The hydrocracking is accomplished on aoncethrough basis, that is, with the 400 F.+ portion of the product notbeing recycled to the hydrocracking zone.

Example 8 The 180-400 F. portion of the product of Example 7 iscatalytically reformed, using a conventional reforming catalyst andconventional reforming conditions, and is found to be a superiorfeedstock for this operation. The catalytic reformate is combined withthe C 180 F. portlion of the product of Example 7, to produce a gasolinepoo.

Example 9 NiO 7.6 M003 27.0 $10 14.4 A1203 51.0

Another portion of the same light cycle oil feedstock that is referredto in Example 4 is passed downwardly through both catalyst beds in thereactor together with added hydrogen, the hydrogen and cycle oilsequentially contacting the catalyst beds, with no product or impurityremoval between beds.

Example 10 The 180-400 F. portion of the product of Example 9 iscatalytically reformed, using a conventional reforming catalyst andconventional reforming conditions, and is found to be a superiorfeedstock for this operation. The catalytic reformate is combined withthe C 180 F.

portion of the product of Example 9 to produce a gasoline pool.

CONCLUSIONS Applicant does not intend to be bound by any theory for theunexpected superior activity and stability of the catalysts of thepresent invention. However, he assumes that the favorable results arelargely attributable to: (1) a different, and more favorable,equilibrium at a given operating temperature for the system consistingof rhenium metal, the various rhenium oxides, the various rheniumsulfides, platinum, palladium or iridium metal, the various oxides ofplatinum, palladium or iridium, the various sulfides of platinum,palladium or iridium, and sulfur and hydrogen, than for the systemconsisting of platinum metal, platinum oxide, platinum sulfide, sulfurand hydrogen, which provides a hydrocracking catalyst superior to theRabo et al. noble-metal-containing catalyst; and (2) an interactionbetween the effect of rhenium or a rhenium compound and said layeredclay-type crystalline aluminosilicate cracking component that producesmore favorable hydrocracking results than are produced by anyinteraction between the effect of rhenium or a rhenium compound and agel-type silica-alumina cracking component such as is used in the Wilsoncatalyst.

It has been known that the process of the present invention hasadvantages over conventional hydrocracking processes, particularly inthat the hydrocracking catalyst comprising said layered clay-typecrystalline aluminosilicate cracking component, a rhenium orrhenium-compound hydrogenating component, and a hydrogenating componentselected from platinum, palladium and iridium and compounds of platinum,palladium and iridium, is nitrogen-tolerant and sulfurtolerant, has ahigh stability, and has high cracking activity.

Although only specific embodiments of the present invention have beendescribed, numerous variations can be made in these embodiments withoutdeparting from the spirit of the invention, and all such variations thatfall within the scope of the appended claims are intended to be embracedthereby.

What is claimed is:

1. A hydrocarbon conversion catalyst comprising: (a) a layeredcrystalline clay-type aluminosilicate component, said layeredaluminosilicate having, prior to drying and calcining of said catalyst,the empirical formula nsiO zAl O mAB :xH O

where the layer lattices comprise said silica, said alumina, and said B,and where n is from 2.4 to 3.0

m is from 0.2 to 0.6

A is one equivalent of an exchangeable cation having a valence notgreater than 2, and is external to the lattice,

B is chosen from the group of negative ions which consists of F, OH,/2O-- and mixtures thereof, and is internal in the lattice, and

x is from 2.0 to 3.5 at 50% relative humidity,

said mineral being characterized by a a spacing at said humidity withinthe range which extends from a lower limit of about 10.4 angstroms to anupper limit of about 12.0 angstroms when A is monovalent, to about 14.7angstroms when A is divalent, and to a value intermediate between 12.0angstroms and 14.7 angstroms when A includes both monovalent anddivalent cations; and (b) 0.01 to 2.0 weight percent, based on saidaluminosilicate component and calculated as the metal, of ahydrogenating component selected from platinum and compounds thereof,palladium and compounds thereof, and iridium and compounds thereof; and(c) 0.01 to 2.0 weight percent, based on said aluminosilicate componentand calculated as the metal, of a hydrogenating component selected fromrhenium and compounds of rhenium.

2. A catalyst as in claim 1, which further comprises a matrix containinga component selected from alumina gel and silica-alumina gel.

3. A catalyst as in claim 7., which further comprises at least onehydrogenating component selected from Group VI metals and compoundsthereof and nickel and compounds thereof.

4. A catalyst as in claim 2, wherein said layered claytype crystallinealuminosilicate cracking component is in particulate form, and isdispersed through said matrix.

5. A catalyst as in claim 2, which further comprises titania.

6. A catalyst as in claim 4, wherein said layered claytype crystallinealuminosilicate cracking component is substantially in the ammonia orhydrogen form and is substantially free of any catalytic metal ormetals, and wherein said hydrogenating components are contained in saidmatrix.

7. A catalyst as in claim 6, which further comprises titania.

8. A catalyst as in claim 6, which further comprises tin or a compoundof tin.

9. A catalyst comprising:

(A) A layer-type, crystalline, clay-like cracking component which priorto drying and calcining of said catalyst has the empirical formula nSiOA1 0 mAB :xH O

where the layer lattices comprise said silica, said alumina, and said B,and where n is from 2.4 to 3.0

m is from 0.2 to 0.6

A is one equivalent of an exchangeable cation having a. valence notgreater than 2, and is external to the lattice,

B is chosen from the group of negative ions which consists of F, OH,/2O- and mixtures thereof,

and is internal in the lattice, and

x is from 2.0 to 3.5 at relative humidity,

said mineral being characterized by a d spacing at said humidity withinthe range which extends from a lower limit of about 10.4 A. to an upperlimit of about 12.0 A. when A is monovalent, to about 14.7 A. when A isdivalent, and to a value intermediate between 12.0 A. and 14.7 A. when Aincludes both monovalent and divalent cations, and

(B) A hydrogenerating component selected from platitinum, palladium andiridium and compounds of platinum, palladium and iridium, in an amountof 0.01 to 2.0 weight percent, based on said cracking component andcalculated as metal, and a hydrogenerating component selected fromrhenium and compounds of rhenium, in an amount of 0.01 to 2.0 weightpercent, based on said cracking component and calculated as metal.

10. A catalyst as in claim 9, wherein said mineral is present in anamount of 10 to 99.9 weight percent, based on the total catalyst.

11. A catalyst as in claim 9, which further comprises a crystallinezeolitic molecular sieve component, in the amount of l to 50 weightpercent, based on the total catalyst.

12. A catalyst as in claim 9, wherein A is chosen from the groupconsisting of H+, NH Na Li+, K+, /;Ca++, Mg++, /;Sr++, and Ba++ andmixtures thereof.

13. A hydrocracking process which comprises contacting a hydrocarbonfeedstock containing substantial amounts of materials boiling above 200F. and selected from the group consisting of petroleum distillates,solventdeasphalted petroleum residua, shale oils and coal tardistillates, in a reaction zone with hydrogen and the catalyst of claim1, at hydrocracking conditions including a temperature in the range 400to 950 F., a pressure in the range 800 to 3500 p.s.i.g., a liquid hourlyspace velocity in the range 0.1 to 5.0 and a total hydrogen supply rate1 7 of 200 to 20,000 s.c.f. of hydrogen per barrel of said feedstock,and recovering from said reaction zone valuable products, includinggasoline.

14. A process as in claim 13, wherein said catalyst further comprises acomponent selected from the group consisting of alumina gel andsilica-alumina gel.

15. A process as in claim 14, wherein said catalyst further comprises atleast one hydrogenating component selected from the group consisting ofGroup VI metals and compounds thereof and nickel and compounds thereof.

16. A process as in claim 13, wherein said hydrocarbon feedstockcontains 0.5 to 1000 p.p.rn. organic nitrogen.

17. A process as in claim 13, wherein said reaction zone contains, inaddition to said catalyst, a separate second catalyst comprising ahydrogenating component selected from Group VI metals and compoundsthereof, a hydrogenating component selected from Group VIII metals andcompounds thereof, and a component selected from the group consisting ofalumina and silica-alumina.

18. A process as in claim 17, wherein said separate second catalyst islocated in said reaction zone in a bed disposed above said catalystcomprising a layered claytype crystalline aluminosilicate crackingcomponent.

19. A hydrocracking process which comprises sequentially contacting ahydrocarbon feedstock and hydrogen with a first bed of catalyst and thenwith a second bed of catalyst, said catalyst beds both being locatedwithin a single elongated reactor pressure shell, said first bed ofcatalyst being located in an upper portion of said shell, the catalystof said first bed comprising a hydrogenating component selected from thegroup consisting of Group VI metals and compounds thereof and Group VIIImetals and compounds thereof and a component selected from the groupconsisting of alumina and silica-alumina, the catalyst of said secondbed being the catalyst of claim 1, maintaining said first bed ofcatalyst and said second bed of catalyst at a temperature in the range400 to 950 F. and a pressure in the range 800 to 3500 p.s.i.g. duringsaid contacting, maintaining the total supply rate of said hydrogen intosaid reactor shell from 200 to 22,000 s.c.f. of hydrogen per barrel ofsaid feedstock, and recovering a gasoline product from the eflluent ofsaid second bed of catalyst.

20. A process as in claim 19, wherein the efiluent from said second bedof catalyst is separated into fractions, including a light gasolinefraction, a heavy gasoline fraction, and a fraction boiling generallyhigher than said heavy gasoline fraction.

21. A process as in claim 20, wherein said heavy gasoline fraction iscatalytically reformed.

22. A process as in claim 20, wherein said fraction boiling generallyhigher than said heavy gasoline fraction is catalytically cracked.

References Cited UNITED STATES PATENTS 3,132,087 5/1964 Kelley et al 2083,140,253 7/1964 Plank et al 208 3,236,762 2/1966 Rabo et al 2081113,252,889 5/1966 Capell et a1 208120 DELBERT E. GANTZ, Primary ExaminerA. RIMENS, Assistant Examiner US. Cl. X.R. 20889; 252-455

